The Alexander Lebedev-owned title has a strategy of targeting education channels, and has previously targeted senior schools and universities.
According to Julia Gosling, i's subscription manager, the move into distributing the title in primary schools comes as "one in ten" secondary schools purchase the title.
She said: "Our new initiative aims to make i available to older pupils in British primary schools. The paper has already shown itself to be a great teaching resource by allowing students and teachers to explore the news quickly in an easy-to-read format.
The moves chimes with a TV campaign for i that kicks off this week and features the same TV spot as before, created by McCann London.
The TV ad will be aired on Channel 4, ITV and Channel 5, along with video-on-demand activity.
It will also be aired on student TV across 68 universities nationwide, as the paper seeks to build its presence in the student market.Follow @nickbatten2